LIQUID-LIQUID

EXTRACTION

Ayu Dahliyanti, M.Eng.

Separation Process
Chemical Engineering
Universitas Pertamina
2019
Recommended Youtube channel for Chemical Engineering students!
 OUTLINE OBJECTIVES
▪ Introduction ▪ To explain the basic principles of
▪ Solvent Selection liquid-liquid extraction
▪ Equipments ▪ To calculate minimum solvent flow
rate
▪ LLE with Ternary System: Hunter-
Nash Method ▪ To calculate the number of
equilibrium stages (N)
▪ Kremser Equation for Dilute LLE

• Chapter 13: Wankat, "Separation Process Engineering Includes Mass

MAIN Transfer Analysis", 3rd Ed., Prentice Hall, 2011
REFERENCES • Chapter 8: Seader, Henley and Roper, “Separation Process Principles”,
3rd Edition, John Wiley and Sons, Inc., 2011
INTRODUCTION Definition:
• Separation of one or more component of a liquid phase (feed)
Basic Principles by contacting it with a second liquid phase (solvent) which is
miscible or partially miscible with at least one feed component.

(Solute +
carrier liquid)

Laboratory
Extraction Column Extraction schematic Extraction process with solvent recovery
INTRODUCTION
LLE with solvent
recovery by distillation

Identify:
1. Solute
2. Carrier liquid
3. Solvent
4. Function of distillation
column (top and bottom)
INTRODUCTION
Other reasons:
LLE vs Distillation

LLE is often preferred

over distillation due to
economic reason to purify
mixture with starting
concentration less than
50%.
INTRODUCTION
Industrial Examples
SOLVENT High selectivity for the solute
SELECTION
Ideal Solvent High capacity for dissolving solute
Characteristics
Minimal solubility in the carrier liquid

Sufficient volatility or density difference between

solute & solvent for easier separation

Low cost

Inert (noncorrosive), nontoxic, nonflammable

SOLVENT SELECTION Example: to extract acetone (Group 3),
we can use solvent from Group 1 and 6
EQUIPMENT
SELECTION FOR LLE

Spray Column
Mixer-settlers

Column with Mechanical Agitator

Centrifugal Extractors
EQUIPMENT
SELECTION FOR LLE

KARRⓇ Column
EQUIPMENT
SELECTION FOR LLE
EQUIPMENT
SELECTION FOR LLE
Algorithm
LLE WITH TERNARY
SYSTEM
Ternary Equilibrium
Data
LLE WITH TERNARY
SYSTEM
Ternary Equilibrium
Data: How to Draw
LLE WITH TERNARY Draw a ternary diagram (including tie lines)
SYSTEM for these equilibrium data of Water (D)-
Ternary Equilibrium Chloroform(S)-Acetone(A) system!
Data
 Solute (A)
LLE WITH TERNARY
SYSTEM
Ternary Equilibrium
Data

Solvent (S) Carrier (S)

 LLE WITH TERNARY Plait point:
SYSTEM Conjugate Line composition of
raffinate &
Interpolating Tie Line extract are equal

Step:
1. Draw lines parallel to the adjacent side
of the triangle from each ends of tie
line (DH-EH, AJ-BJ, and so on)
2. Connect the dots where the lines
intersect to make a conjugate line.
3. Interpolate new tie lines using
conjugate line.

method of International Critical

Tables, Vol. III, McGraw Hill, New
Other resources: https://www.youtube.com/watch?v=n7DPiuHllZE York, p. 393 (1928)
LLE WITH TERNARY Number of Equilibrium Stages:
SYSTEM Hunter-Nash Method
A = Solute
C = Carrier Liquid
S = Solvent
LLE WITH TERNARY Example:
A liquid Feed (F) which contain solute A is to be extracted by Solvent S.
SYSTEM If mass fraction of acetone in the raffinate = 0.025, how many
equilibrium stages are needed for this operation?
Number of Feed and Solvent compositions are as follows:
Equilibrium Stages:
Hunter-Nash Method

Step:
1. Draw equilibrium data in ternary diagram
2. Draw the known feed, solvent, & raffinate/extract points in
the ternary diagram
LLE WITH TERNARY Mixing Point represent the combined composition of feed F and solvent S
SYSTEM Method 1: material balance
Total Balance: 𝐹 + 𝑆 = 𝑀 = 𝐸1 + 𝑅𝑁
Number of
Equilibrium Stages: 𝑀 = 250 + 100 = 350𝑘𝑔

Hunter-Nash Method Component Balance:

Step:
3. Determine Mixing Point (M) composition by
material balance or Inverse Lever Rule
Feed Solvent Mixing
(F) (S) Point (M)
XA 0.24 0.00 0.171

XC 0.74 0.00 0.543

XS 0.00 1.00 0.286

Flow 250 100 350 Now we can draw point M on the ternary diagram
rate
LLE WITH TERNARY Mixing Point is always located on the straight line connecting F and S!

SYSTEM
Number of
Equilibrium Stages:
Hunter-Nash Method
Feed Solvent Mixing
(F) (S) Point (M)
XA 0.24 0.00 0.171

XC 0.74 0.00 0.543

XS 0.00 1.00 0.286

Flow 250 100 350

rate
LLE WITH TERNARY Method 2: Inverse lever rule

SYSTEM Since Mixing Point is always located on the straight line connecting F and S,
we can determine length ratio of S-F and S-M lines:
Number of
Equilibrium Stages:
Hunter-Nash Method
Step:
3. Determine Mixing Point (M) composition by
material balance or Inverse Lever Rule Length Length
of M-F of S-F
Feed Solvent Mixing line line
(F) (S) Point (M)
XA 0.24 0.00 0.171
Now we can locate point M and read the composition
XC 0.74 0.00 0.543

XS 0.00 1.00 0.286

Flow 250 100 350

rate
LLE WITH TERNARY Mixing Point is always located on the straight line connecting F and S!

SYSTEM
Number of
Equilibrium Stages:
Hunter-Nash Method
Feed Solvent Mixing
(F) (S) Point (M)
XA 0.24 0.00 0.171

XC 0.74 0.00 0.543

XS 0.00 1.00 0.286

Flow 250 100 350

rate
LLE WITH TERNARY E1 and RN is always located on the equilibrium curve
SYSTEM
Material balance
Number of
Equilibrium Stages:
Hunter-Nash Method
Step:
4. Determine Extract (E1) and Raffinate (RN)
Composition
Feed Solvent Mixing Extract Raffinate
(F) (S) Point (M) (E1) (R) Since (xA)RN = 0.025, from
XA 0.24 0.00 0.171 0.025 material balance we can get
raffinate composition as
XC 0.74 0.00 0.543 0.90 follows from its location in
the equilibrium curve:
XS 0.00 1.00 0.286 0.075

Flow 250 100 350 151.4 198.6

rate
 LLE WITH TERNARY E1 can be determined by making a straight line from RN through M until it
reaches equilibrium curve on the opposite side.
SYSTEM
Number of
Equilibrium Stages:
Hunter-Nash Method
We can read
Step: E1 composition
4. Determine Extract (E1) and Raffinate (RN)
Composition
Feed Solvent Mixing Extract Raffinate
(F) (S) Point (M) (E1) (R)
XA 0.24 0.00 0.171 0.364 0.025

XC 0.74 0.00 0.543 0.075 0.90

XS 0.00 1.00 0.286 0.561 0.075

Flow 250 100 350 151.4 198.6

rate
LLE WITH TERNARY Number of Equilibrium
SYSTEM Stages: Hunter-Nash Method
Step:
5. Draw operating lines by
extending lines E1-F and
S-RN until intersect at
point P
LLE WITH TERNARY Number of Equilibrium
SYSTEM Stages: Hunter-Nash Method
Step:
5. Stepping of stages by using
both tie lines and operating
point (P) in turn.

Start at E1, Stop at RN

Number of
equilibrium stage =
Number of tie line
used, here N=2.8
LLE WITH TERNARY SYSTEM • Minimum solvent requirement for desired separation
• Occurs when tie line coincides with operating line
Hunter-Nash Method: Minimum
• Resulting in infinite number of stages → higher capital cost.
Solvent Flow Rate
How to:
1. Draw extended line from S through RN (OL line)
2. Extend tie line which passes through feed point to obtain Pmin
and E1,min (interpolate if not readily available)
3. Use all compositions to determine Mixing point (Mmin) and
solve the following mass balance.
Exercise
Read composition in each stage from the diagram

Flow rate per stage:

F + En = Rn-1 +E1
DILUTE LLE When the concentration of solute in the feed is relatively low, Kremser
equation can be used to calculate N and product composition.
Kremser Equation With several assumptions:
• Operation is isothermal and isobaric
• R=F=constant and E=S=constant
• Equilibrium line is linear

Equilibrium relation is represented Kremser equation:

R0, x0 E1, y1 by distribution ratio, Kd:

For preliminary design,

practical value that is
commonly used is
(mE/R)min = 1.3
EN+1, yN+1 RN, xN
DILUTE LLE
Distribution coefficient for
dilute LLE

Values of Kd are tabulated in

various references, such as Perry’s
Handbook of Chemical Engineers
DILUTE LLE
EXERCISE